WO1988002378A1 - Procede de polymerisation d'olefines - Google Patents

Procede de polymerisation d'olefines Download PDF

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Publication number
WO1988002378A1
WO1988002378A1 PCT/JP1987/000696 JP8700696W WO8802378A1 WO 1988002378 A1 WO1988002378 A1 WO 1988002378A1 JP 8700696 W JP8700696 W JP 8700696W WO 8802378 A1 WO8802378 A1 WO 8802378A1
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Prior art keywords
group
compound
organic
zirconium
bis
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PCT/JP1987/000696
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English (en)
Japanese (ja)
Inventor
Toshiyuki Tsutsui
Akinori Toyota
Norio Kashiwa
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Mitsui Petrochemical Industries, Ltd.
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27477101&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1988002378(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from JP23124286A external-priority patent/JPH0780931B2/ja
Priority claimed from JP61231243A external-priority patent/JPH0780937B2/ja
Priority claimed from JP61293446A external-priority patent/JP2502071B2/ja
Application filed by Mitsui Petrochemical Industries, Ltd. filed Critical Mitsui Petrochemical Industries, Ltd.
Priority to AT87906209T priority Critical patent/ATE89836T1/de
Priority to KR1019880700560A priority patent/KR920001352B1/ko
Priority to DE8787906209T priority patent/DE3786013T2/de
Publication of WO1988002378A1 publication Critical patent/WO1988002378A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

Definitions

  • the present invention relates to a method for polymerizing a olefin. More specifically, when an oligomer is polymerized by a catalyst exhibiting excellent polymerization activity in the use of a small amount of aluminoxane and has a narrow molecular weight distribution and is applied to the copolymerization of two or more types of olefins,
  • the present invention relates to a polymerization method capable of producing an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution.
  • a titanium-based etchant comprising a titanium compound and an organic aluminum compound.
  • a method is known in which a copolymer of ethylene or ethylene and one-year-old olefin is present in the presence of a vanadium-based solvent composed of a vanadium compound and an organic compound.
  • ethylene ⁇ or — olefin copolymers obtained with titanium-based catalysts had a wide molecular weight distribution and composition distribution, and were inferior in transparency, surface non-adhesion, and mechanical properties.
  • the ethylene ⁇ olefin copolymer obtained with a vanadium-based solvent has a narrower molecular weight distribution and composition distribution than those obtained with a titanium-based catalyst, and has transparency, surface non-adhesion, Although the mechanical properties are considerably improved, they are still insufficient for applications requiring these properties. Therefore, there is a need for a one-year-old olefin polymer with further improved performance, especially an ethylene-one year-old olefin copolymer.
  • zirconium conversion is a new Ziegler-type polymerization catalyst. Catalysts consisting of compounds and aluminoxanes have recently been proposed.
  • JP-A-58-19309 discloses the following formula:
  • JP-A-53-35292 discloses the following formula:
  • n 2-40 and R 3 is ⁇ C 3 alkyl
  • a linear aluminoxane represented by the following formula:
  • n and R 3 are the same as described above.
  • the invention relating to a method for producing a cyclic aluminoxane represented by-is described.
  • the gazette states that, for example, a mixture of methylaluminum oxane and a bis (cyclopentajenyl H tertiary compound) of titanium or zirconium produced by the same production method is used to polymerize an orifice. It is stated that more than 25 million s of polyethylene can be obtained per transition metal per hour and per hour.
  • Japanese Patent Application Laid-Open No. 60-350005 discloses the following formula:
  • a method is disclosed in which an aluminoxane compound represented by the following formula is first reacted with a magnesium compound, then the reaction product is chlorinated, and further treated with a compound of Ti, V, Zr, or to produce a polymerization catalyst for an olefin.
  • the publication describes that the medium is particularly suitable for copolymerization of a mixture of ethylene and C 3 -C 12 olefin.
  • Japanese Patent Application Laid-Open No. 60-350006 discloses that a catalyst system for producing a reactor polymer is composed of two or more different kinds of transition gold-based monomers, G- or tri-metals. -Combinations of cyclopentagenenyl or derivatives thereof ( a ) and alumoxane (aluminum / oxane) (b) are disclosed.
  • Example 1 of the publication discloses that ethylene and propylene were polymerized using bis (pentamethylcyclopentagenenyl) zirconium dimethyl and alumoxane as erosion media to obtain a number average molecular weight of 15,300, a weight average molecular weight of 36, It is disclosed that a polyethylene containing 400 and 3.4% of a propylene component was obtained.
  • Example 2 ethylene and propylene were polymerized using bis (pentamethylcyclo ⁇ pentagenenyl) zirconium dichloride, bis (methylcyclopentagenenyl) zirconium dichloride and alumoxane as catalysts.
  • Example 3 the molecular weight distribution (3 ⁇ 4u / Zn) of 4.57 and the soluble portion of the ⁇ -pyrene component of 20.6 mol% and the molecular weight distribution of 3 ⁇ 04 and the insoluble portion of the ⁇ -pyrene component of 2.9 mol% were obtained.
  • the blend of the LLDPE and the ethylene-propylene copolymer is described.
  • JP-A-60-35007 discloses that ethylene alone or in combination with a olefin having 3 or more carbon atoms has the following formula:
  • R 5 is an alkyl group having 1 to 5 carbon atoms
  • ⁇ is an integer from 1 to about 20
  • R 5 where the definitions of R 5 and n are the same as above
  • the polymer obtained by the method has a weight average molecular weight of about 500 to about 1.4 million and a molecular weight distribution of 1.5 to 4.0.
  • Japanese Patent Application Laid-Open No. Sho 60-35008 discloses that a catalyst having at least two kinds of meta-acene and alumoxane is used to obtain polyethylene or ethylene having a wide molecular weight distribution and ethylene and CaC. It is described that the ⁇ -olefin copolymer can be produced.
  • the publication discloses that the above copolymer has a molecular weight distribution (MwZMn) 2 -50.
  • the catalyst formed from these transition metal compounds and aluminoxane is more excellent in the polymerization activity than the catalyst system known from U.S.A.
  • a method using a catalyst formed from an aluminoxane and a solid catalyst component in which the transition metal compound is supported on a porous non-oxide carrier such as silica, silica * alumina, and alumina is described. It has been proposed in the above-mentioned JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008. Further, JP-A-6-131404, JP-A-6-130610 and JP-A-60-106808 disclose similar porous non-oxide carriers.
  • a method using a supported solid edible medium component has been proposed. Further, a method of polymerizing olefins using a catalyst formed from a mixed organic aluminum compound comprising a transition metal compound or an aluminum / oxane and an organic or aluminum compound is disclosed in Japanese Patent Publication No. 60-260602. And Japanese Patent Application Laid-Open No. Sho 60-130604.
  • JP-A-60-260602 discloses that '
  • R 3 is C t -C 10 alkyl, cycloalkyl or aryl, X is halogen, and
  • n is a number from 1 to 3
  • a method for producing vorolefin by polymerizing olefin is disclosed.
  • Examples in the publication include a method in which toluene 40 is used as a polymerization medium.
  • An example is described in which ethylene is polymerized in a system containing 3 mmol of luminoxane, 3 mmol of triethylaluminum, and 0.003 mmol of bis (cyclopentagel) zirconium chloride.
  • M is Ti, ⁇ 1 ⁇ or 1 1 £, and
  • R ' 0 and R] 1 each H, halogen
  • R 12 is methyl or ethyl
  • X 1 is halogen
  • R 13 is ⁇ C ,.
  • X 2 is alkyl or cycloalkyl, X 2 is halogen, and
  • n is a number from 1 to 3
  • Polyolefin is polymerized using a catalyst consisting mainly of A method for manufacturing a component is disclosed.
  • the amount of aluminoxane used was 4.5 mmol (Examples 1 to 4 and 8), 3.6 mi '/ mol (Example 5), 3.2 mmol / 40 toluene 40 as a polymerization medium.
  • Examples of 5 mimol (Example 6), 10.0 mi '/ mol (Example 7 of realba) and S.0 mi'; molar (Example 3) are described.
  • An object of the present invention is to provide an orefin copolymer having a narrow molecular weight distribution and a narrow molecular weight distribution and composition distribution when applied to copolymerization of two or more types of orefins, particularly a narrow molecular weight distribution and composition distribution.
  • An object of the present invention is to provide a method for producing an ethylene-olefin copolymer having a high molecular weight with excellent polymerization activity by using a small amount of aluminoxane.
  • the present invention relates to a method for producing an ethylene polymer or ethylene-olefin copolymer having excellent properties and a poor molecular weight distribution and / or composition distribution.
  • the erosion medium of the present invention can be formed from a solid catalyst component ( ⁇ ), an aluminoxane ( ⁇ ), and an organic aluminum compound (C) having a hydrocarbon group other than an ⁇ -alkyl group.
  • the sensitizer component ( ⁇ ) is a solid erosion component in which a transition metal compound of the VB group is supported on a carrier.
  • the transfer metal of Group IV of the Periodic Table IV in the catalyst component (II) is preferably selected from the group consisting of, for example, titanium, zirconium and hafnium. Of these, titanium and zirconium are more preferred, with zirconium being particularly preferred.
  • transition metal compound of Group 1VB of the periodic table in the catalyst component (II) for example, a transition metal compound having a group having a conjugated electron as a ligand can be mentioned as a preferable example.
  • a compound having a conjugated electron with a group having an electron as a ligand is represented by the following formula (I)
  • R ′ represents a cycloalkadienyl group
  • R 2 , R 3 and R 4 are the same or different and are a cycloalkadienyl group, an aryl group, an alkyl group, a cycloalkyl group, Ararukiru group, a halogen atom, water atom, Kiichi oR a, is an SR b or one NR C 2,
  • R a , R b and R c are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group;
  • Me is zirconium, titanium or hafnium
  • k 1, 2, 3, or 4
  • Examples of the cycloalkadienyl group represented by R 1 include a cyclopentagenyl group, a methylcycloventenyl group, an ethynolecyclopentadienyl group, a dimethylcyclopentagenenyl group, an indenyl group, and a tetrahydroindenyl group. Examples can be given.
  • the cycloalkadienyl group represented by R 2 , R 3 and R 4 the same groups as described above can be exemplified.
  • Preferred examples of the aryl group represented by R 2 , R 3 and R 4 include a phenyl group and a tolyl group.
  • aralkyl group examples include a benzyl group and a neophyl group.
  • alkyl group examples include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group and a benzyl group. Can be done. ⁇
  • cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norponyl group and the like.
  • halogen atom examples include fluorine, chlorine, and bromine.
  • Examples of the organic silyl groups of R a , R b and R c include, for example, a trimethylsilyl group, a triethylsilyl group, a phenyldimethylsilyl group, and a diphenylmethyl group. Tilsilyl groups and triphenylsilyl groups can be mentioned.
  • examples of the zirconium compound in which Me is zirconium include the following compounds.
  • Bis cyclopentagenenyl 2-ethylhexoxy zirconium Biscyclopentadienyl 7 enoxy zirconium chloride ps cyclopentagenenyl cyclohexoxy zirconium chloride Bis (cyclopentagenenyl) phenylmethoxyzirconium chloride bis (cyclopentagenyl) methylzirconiumphenylmethoxide bis (cyclopentagenenyl) trimethylsiloxyzirconium chloride,
  • Ethylenebis (4-methyl-1-indenyl) zirconium dichloride Ethylenebis (5-methyl-1-indenyl) zirconium dichloride ⁇ Ethylenebis (6-methyl-1-indull) zirconium dichloride
  • Ethylenebis (indenyl) methoxyzirconium chloride ⁇ -ethylene, ethylenebis (indenyl) ethoxyzirconium chloride, ethylenebis (indenyl) methylzirconium ethoxide, ethylenebis (4,5,6,7-tetraethyl) Draw 1 indenyl) zircon Numju's methoxide,
  • examples of the titanium compound in which Me is titanium include the following compounds.
  • Me is hafnium, and the following compound can be exemplified as the hafnium compound.
  • the transition metal compound of Group B of the periodic table may be previously treated with an organometallic compound or a halogen-containing silicon compound before being supported.
  • Organic gold compounds include, for example, aluminum, aluminum, organic magnesium, organic zinc, and lithium. Wear. Of these, organic aluminum compounds are preferred.
  • organic aluminum compound examples include trifluoroalkyl aluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum; alkenylaluminum such as sobrenylaluminum; dimethylaluminummethod.
  • Dialkylaluminum alkoxides such as oxides, getylal 5 "diammoxides, and dibutylaluminum butoxide; alkylaluminum alkoxides, such as methyl alcohol dimethyl sesquimethoxide, ethyl aluminum dimethyl sesquioxide sesqui alkoxy de;..
  • R 1 and R 2 ho alkyl group Aluminum: dimethylaluminum chloride, getylal Dialkylaluminum halides, such as aluminum chloride, dimethylaluminum bromide; alkylaluminum halides, such as methylaluminum sesquichloride, ethylaluminum sesquichloride; methylaluminum dichloride, ethylaluminum dichloride Partially halogenated alkyl aluminum, such as alkyl alcohol, such as metal halide, etc., can be exemplified.
  • Trialkylaluminum and dialkylaluminum chlorides are preferred, with trimethylaluminum, triethylaluminum and dimethylaluminum chloride being particularly preferred.
  • organic boron compound for example, triethylboron can be exemplified as a preferable compound.
  • organomagnesium compound examples include ethyl butyl magnesium, di-n-hexyl magnesium, ethyl ethyl nesium bromide, and phenyl ethyl magnesium.
  • organomagnesium compound examples include magnesium chloride and benzylmagnesium chloride.
  • getyl zinc can be exemplified as a preferable example.
  • organolithium compound examples include methyllithium, butyllithium, and phenyllithium.
  • organic metal compound (C) organic aluminum is preferable.
  • halogen-containing silicon compounds as processing agents! For example, the following expression (GO '
  • Y is a chlorine atom or a bromine atom
  • R 5 and R s are each independently a hydrogen atom
  • Carbon atom 1- an alkyl group, aryl group of L2 or a carbon number 3-: cycloalkyl group of I2,
  • d is a number from 1 to 4,
  • e is a number from 0 to 4,
  • the compound represented by is preferably used.
  • Such compounds include, for example, silicon tetrachloride, silicon tetrabromide, silicon trichloride, methyl silicon trichloride, ethyl silicon trichloride, propyl silicon trichloride, phenyl silicon trichloride, cyclohexyl silicon trichloride.
  • the mixing ratio of the dominant metal compound and the inorganic carrier is 0.5 to 50, preferably 1 to 30, more preferably 1 to 30 as the gram number ratio of the millimol Z carrier of the organic gold compound. It is in the range of 1.5 to 20.
  • the treatment of the inorganic carrier with the organometallic compound in the catalyst component (A) is performed by dispersing the carrier in an inert solvent, adding one or more of the above organometallic compounds, and using 0 to 120, Preferably at a temperature between 10 and 100, more preferably at a temperature between 20 and 90, between 10 minutes and 10 hours, preferably between 20 minutes and 5 hours, more preferably between 30 minutes and 3 hours. It can be carried out by treating under normal pressure, reduced pressure, or under increased pressure.
  • the inert solvent examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane and isooctane; and alicyclic hydrocarbons such as cyclohexane.
  • the mixing ratio of the halogen-containing silicon compound 'and the inorganic carrier in the above treatment is 0.001 to 10 mol, preferably 0.01 to 50 mol, of the halogen-containing silicon compound per gram of the carrier compound. Mole, more preferably in the range of 0.05 to 1 mole. Further, it is preferable to remove the liquid part containing the surplus halogen-containing silane compound after the above-mentioned treatment from the reaction mixture by a method such as passing or tilting.
  • an inert solvent may be used.
  • the inert solvent include aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as pentane, hexane, isooctane, decane and dodecane.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as pentane, hexane, isooctane, decane and dodecane.
  • examples thereof include alicyclic hydrocarbons such as hydrogen and cyclohexane, and halogenated hydrocarbons such as chlorobenzene and ethylenedichloride.
  • the inert metal when the transition metal compound is a liquid substance, the inert metal may or may not be used when the transition metal compound is a liquid substance in supporting the inorganic carrier with the group B transition metal compound.
  • the transferred metal compound is solid at room temperature! In the case of a solid, it is generally preferable to use an inert solvent capable of dissolving the transfer metal compound.
  • the inert solvent that may be used when treating a rodless carrier with a halogen-containing silicon compound can be exemplified in the same manner.
  • aromatic hydrocarbons such as benzene and toluene or halogenated hydrocarbons such as chlorobenzene are preferable.
  • the amount of the transition metal compound used in the supported anti-ife is preferably 0.001 to 500 millimoles, more preferably 0.01 to 100 millimoles per gram of the radioactive carrier, Particularly, the range of 0.1 to 50 millimol is preferable.
  • the amount of the inert solvent used in the above-mentioned supporting reaction is 0.5 to 100 m per 1 s of the inorganic carrier treated with the ⁇ -gen-containing silane compound, preferably 1 to 100 [a £, especially in the range of 2 to 50 is preferred.
  • the supporting reaction may be carried out by mixing the inorganic carrier and the transfer metal compound at 0 to 200, preferably at 0 to 100, and more preferably at 20 to 80. It can be performed by contact mixing at a temperature for 1 minute to 10 hours, 5 minutes to 5 hours, 10 minutes to 3 hours.
  • the solid catalyst component (A) is a carrier in which a compound of a transition metal of the YB group in the periodic table as described above is supported on a carrier.
  • a granular or fine solid having a particle size of 10 to 300 "l ⁇ , more preferably 20 to 200" HI is preferably used.
  • a small amount of Na 2 C0 3 in the inorganic oxide K 2 C0 3, CaC0 3 , MsC0 3, Na 2 S0 4, A1 2 (S0 4) 3, BaS O "KN 0 3, Ms (N 0 3) 2, A1 (N0 3 ) 3, Na 2 0, K 2 0, L i 2 0 such carbonates, may safely be contained sulfates, nitrates, oxides component.
  • the porous inorganic carrier has a force f that varies in properties depending on its type and manufacturing method, and the carrier preferably used in the present invention has a specific surface area of 50 to 100 m 2 / s, more preferably: L 00 to 7 0 0 [ ⁇ 2 ⁇ , the pore volume is 0.3 to 2.5 c «i 2 / s.
  • the carrier is usually from 150 to 100, preferably 2 It is used after firing at 00 to 800.
  • the periodic table The transfer compound of the FB group is 3 X in terms of the transfer metal atom per 1 s of the organic support treated with the organometallic compound. 10- 3 to 3 Mi Riguramu atoms, preferably 5 X 10-3 a stone 2 Mi Riguramu atoms, more preferably 1 X 10 one from 2 - is the tooth 1 Mi Riguramu atom bearing.
  • the transfer metal compound is usually 0.005 to 5 mol, preferably 0.01 to 1 mol. ) 1 mmol, particularly preferably 0.03
  • ⁇ Divider component (B) is an aluminum / alkaline b.
  • the aluminoxane used as the erosion medium component (B) includes, for example, the following formula (I)
  • R R where R is a hydrocarbon group
  • X is a halogen atom, and a and b are each independently a number from 0 to 80, provided that a and b are not simultaneously zero (where the degree of polymerization is a + b + 2) or (I)
  • R is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group.
  • the cycloalkyl group is preferably, for example, a cyclopentyl group, a cyclohexyl group, etc.
  • the aryl group is, for example, a phenyl group or a tril group
  • the aralkyl group is, for example, Preferable are a benzyl group, a neofil group, etc. Among these, an alkyl group is particularly preferable.
  • X is a haloden atom, for example, fluorine, chlorine, bromine, or iodine, and chlorine is particularly preferable.
  • a and b are each independently a number from 0 to 80. However, a and b are not 0 at the same time. When b is 0, the above equation ( ⁇ ) becomes the following equation ( ⁇ ) —1
  • R where the definitions of R and a are the same as described above, and are represented by the following. Also, the above formula (EI) is represented by the following formula ( ⁇ ) —1
  • R Here, the definitions of R and a are the same as described above.
  • -a is preferably 0 to 40, more preferably 3 to 30.
  • b is preferably 40 to 40, and more preferably 3 to 30.
  • the value of a + b is preferably 4 to 50, and more preferably about 8 to 30.
  • A1— means that even if they are connected in blocks
  • R 7 is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms,
  • Z is a halogen atom
  • f is a number from 1 to 3
  • organic aluminum compound represented by the following formula.
  • organic aluminum compounds include, for example, trimethylaluminum, triethylaluminum, tributylaluminum, and trihexyl.
  • examples include aluminum, getyl aluminum chloride, and ethyl aluminum sesquik mouth light.
  • the halogenated aluminoxane and the organoaluminum compound are as follows: 1 to 1 mole of the organic aluminum compound per 1 mole of A atom in the halogenated aluminoxane; It is preferably used in an amount of from 0.3 to 3.0 mol, particularly preferably from 0.5 to 2.0 mol.
  • Examples of the method for producing the aluminoxane or the halogenated aluminoxane include the following methods.
  • the aluminoxane may contain a small amount of an organic metal component.
  • the catalyst component (C) is an organic aluminum compound having a hydrocarbon group other than an n-alkyl group.
  • hydrocarbon group other than the n-alkyl group include an alkyl group having a branched chain such as dialkyl, a cycloalkyl group, and an aryl group.
  • organic aluminum compound examples include trisopropyl aluminum, trisobutyl aluminum, Tri 2-methylbutylaluminum, Tri3-methylbutylaluminum, Tri2-methylpentinole aluminum, Tri3-methylpentylaluminum, Tri4-methylpentylaluminum
  • Trialkylaluminium such as tri-methylhexyl aluminum, tri-2-methylhexyl aluminum, tri-methylhexyl aluminum
  • trialkylaluminium such as tricyclohexyl aluminum
  • alkyl aluminum alkoxides such as n-isopropoxide.
  • the polymerization of the olefin is carried out by any of a liquid phase polymerization method such as a slurry polymerization method and a solution polymerization method, or a gas phase polymerization method.
  • prepolymerization may be performed using a small amount of olefin before polymerization of olefin.
  • the prepolymerization is carried out (1) without solvent or (2) in an inert hydrocarbon medium.
  • the method (1) is preferable.
  • the catalyst components (A) and (B) are first mixed in an inert hydrocarbon medium, and then the temperature is lowered to room temperature or elevated, and the solvent is removed at normal pressure or reduced pressure using, for example, an evaporator.
  • the molar ratio of the aluminum atom of the catalyst component (B) to the transition metal atom of the catalyst component (A) (AAZ transition metal atom) is 20 to 5,000, preferably 25 to 2,000, More preferably, it is in the range of 30 to 1,000.
  • the prepolymerization temperature ranges from not more than 20 to 70, preferably from not more than 10 to 60, more preferably not from 0 to 50.
  • the treatment can be performed either in a batch system or a continuous system, and can be performed under reduced pressure, normal pressure or increased pressure.
  • a molecular weight modifier such as Eizo may be co-present, but at least
  • the limiting viscosity [] measured in decalin at 135 is more than 0.2 d ⁇ / s , preferably 0.5 to 20 d ⁇ s .
  • the ratio of the transition metal compound (A) to be used is usually 10 1 as the concentration of the ⁇ transfer metal ⁇ atoms in the polymerization reaction system. 8 to 1 0 one 2 g atoms / preferably 1 0 one 7 to 1 0-3 gram atom / ⁇ range.
  • the amount of the aluminoxane (B) to be used is 3 milligrams or less, preferably 0.1 to 2.5 milligrams, in terms of aluminum atoms in the system. Is in the range of 0.2 to 2 milligram atoms ⁇ .
  • the alcohol in the reaction system The ratio of the aluminum atom of the aluminoxane component (B) to the total amount of aluminum atoms of the minoxane component (B) and the aluminum compound component (C;) is usually about 20 to 8%. 0%, preferably 25 to 75%, particularly preferably 30 to 70%, and the proportion of aluminum atoms of the aluminum compound component (C) is usually 20% in response to this amount.
  • the ratio of the amount of aluminum atoms of the aluminoxane component (B) and the organoaluminum compound component (C) to the number of aluminum atoms in the reaction system is usually 20 to 10%. It is preferably in the range of 0.000 to 500, particularly preferably in the range of 100 to 2000.
  • the polymerization or copolymerization of the olefin can be advantageously carried out.
  • a transfer metal compound of an erosion medium system it is used and is selected from the group consisting of transition metals of Group 1 of the Periodic Table, oxygen, sulfur, nitrogen and violet.
  • the inorganic carrier is not necessarily used. It has been revealed that even when a transition metal compound is not supported, excellent activity is exhibited similarly to the erosion medium system comprising the components (A), (B) and (C).
  • a conjugated metal compound comprising a ligand having r atoms, (B) aluminoxane, and
  • transition metal compound (A) ′ for example, the following formula ( ⁇ ⁇
  • R M is cycloalkadienyl
  • R ′ 2 is a group selected from the group consisting of 10 R a , — SR b , and 1 Pfd
  • R ′ 3 and R 14 are Independently of one another, cycloalkadienyl, aryl, aralkyl, halogen or hydrogen, R a , R b and
  • R c is alkyl, cycloalkyl, aryl, aralkyl, or organosilyl
  • Me is zirconium, titanium or hafnium
  • n 0, 1 or 2;
  • the compound represented by is preferably used.
  • Bis-cyclopentagenenyl) methizolezirconium butoxide bis-cyclopentagenenyl) ethyldino-le-dimethyl methoxide, bis-cyclopenta-gen-yl) phenyl zirconium methoxide, bis-cyclopentene benzyl benzyl methoxide Oxide, pismethylcyclopentagenenyl) ethoxyzirconium chloride, pisindenyl) ethoxyzirconium chloride,
  • Zirconium compounds such as ethylenbis (4,5,6,7-tetrahydro-1-indenyl) ethoxy zirconium chloride: Biscyclopentagenenyl) ethoxytitanium chloride,
  • Hafnium compounds such as bis (cyclopentagenol) phenoxyhafnium chloride, bis (cyclopentenyl) thiophenylhafnium chloride, bis (cyclopentagenenyl) bis (getylamide) hafnium,
  • an erosion medium system comprising the above components ( ⁇ ), ( ⁇ ) and (C) and an erosion system comprising the above components ( ⁇ ) ′, ( ⁇ ) and (C)
  • the catalyst components ( ⁇ , (8) and ((anti)) 3 ⁇ 4 may be respectively supplied to the system, and a mixture of two catalyst components in advance and the remaining one catalyst component May be respectively supplied to the reaction system, or all of the erosion medium components may be premixed and then supplied to the reaction system.
  • the erosion medium components (A) and ( B) is preferably premixed
  • the concentration of the transition metal atom is usually from 2.5 ⁇ 10— to 1.5 ⁇ 10 g atom Z, preferably from 5.0 ⁇ 10 to 1.0 ⁇ 10 ⁇ ′.
  • the concentration of the aluminum oxane is usually 0.05 to 5 gram atoms Z, preferably 0.1 to 3 gram atoms // in terms of aluminum atoms.
  • the concentration in the premix is usually between 50 and 100, and the mixing time is usually between 0.1 minute and 50 hours.
  • any of the catalysts of the present invention described above ii can be advantageously used for homopolymerization or copolymerization of the olefin.
  • it is effective for the production of ethylene copolymers and copolymers of ethylene with ethylene.
  • the olefins that can be used in the present invention include ethylene and olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1--' 1-octane, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octanedecene, and 1-decocene.
  • the polymerization of the olefin is usually carried out in a gas phase or in a liquid phase, for example, in a slurry.
  • an inert hydrocarbon may be used as a solvent, or the olefin itself may be used as a solvent.
  • the hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, cyclopentane, methylcyclopi-pentane, and cyclopentane.
  • Examples include alicyclic hydrocarbons such as mouth hexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, and xylene, and petroleum fractions such as gasoline, kerosene, and shoe oil.
  • alicyclic hydrocarbons such as mouth hexane and cyclooctane
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • petroleum fractions such as gasoline, kerosene, and shoe oil.
  • aliphatic hydrocarbons, aliphatic hydrocarbons, and petroleum fractions are preferred.
  • the polymer temperature is usually from 150 to 120, preferably from 0 to 100.
  • the method of the present invention to 1 0 one 8 to normal ho proportion as the concentration of ⁇ transfer metal atom in the polymerization reaction system ⁇ gold sake compound of practicing in the slurry first polymerization or gas phase polymerization 1 0 one 2 g atoms / preferably ho 1 0 one 7 to 10-3 gram atom / ⁇ Bruno - is enclosed.
  • aluminoxane may be used additionally or not, but in order to obtain a polymer having excellent powder properties, it is preferable not to use aluminum oxane.
  • the polymerization pressure is usually from atmospheric pressure 1 0 0 k s / C 2 , is not preferred Ho 2 to pressurized conditions 5 O k sr / cm 2, the polymerization, the surface component type, semi ⁇ expression of communication ⁇ Either method can be used.
  • the olefin polymer in the present invention particularly ethylene polymerization or olefin polymerization to become ethylene, adhesion of the polymer to the reactor becomes ineffective.
  • the copolymer is excellent in powder properties, has a narrow molecular weight distribution, and can be used for copolymerization of two or more types of olefins, an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained.
  • Mw ZMn value is carried out as follows in accordance with “Gel Per Meier-Clon ⁇ Chromatography” published by Takeuchi and Maruzen. .
  • Chrotaatograph is measured and a calibration curve is created for the correlation diagram between molecular weight M and Ev (E1 unit volume).
  • concentration at this time shall be 0.02wt%.
  • a GPC chromatograph of the sample is obtained by GPC measurement, and a 3 ⁇ 4-average molecular weight Mn and a weight-average molecular weight Mw in terms of polyethylene are calculated according to the above (1), and an Mw / Mn value is obtained.
  • the PC measurement conditions are as follows.
  • the test was performed under the following conditions.
  • ⁇ value of the ethylene copolymer of the present invention is defined as follows.
  • [rho epsilon represents the molar fraction of the ethylene component in the copolymer
  • [rho Omega Ho Do - O Les 7 shows the molar fraction of the fin component
  • P QE guess of the total dyad chain - ⁇ Shows the mole fraction of ethylene chains
  • the B value is a measure of the distribution of each monomer component in the copolymer armor, and is GJ Ra / (MacrofnoIecules, 10, 7 7 3 (1 9 7 7)), J. C. Randal 1 (Macromolecules, 1-5 '35 (1 98 2)) ⁇ J ..
  • P E from the-spectrum Le is calculated Ri by the P 0 and P () E to determined Mel it.
  • the temperature was raised to 40, and the reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation was performed excessively, and toluene was further removed by using a liquid to obtain white solid aluminoxane 13s.
  • the molecular weight determined by freezing point depression in benzene was 930, and the tn value shown in the catalyst component [B] was 14.
  • Toluene 50,000 [ ⁇ ] was charged into a glass autoclave having an internal volume of 1 which had been sufficiently purged with nitrogen, and a mixed gas of ethylene and propylene (each of 120
  • Example 2-3 polymer was hardly obtained by Comparative Example 2 6
  • Comparative Example 8 In the polymerization of Example 1, the same procedure as in Example 1 was carried out except that tris-butylaluminum was not used, aluminoxane was used in an amount of 2.5 milligram atoms in terms of aluminum atoms, and polymerization was carried out for 30 minutes. 22.8 s of a polymer having an MFR of 1.6 3 g / 1 Oarin, an ethylene content of 82.8 mol%, ⁇ / ⁇ 1.32, and a ⁇ value of 1.14 were obtained.
  • Example 15 bis (cyclo ⁇ pentagenenyl) zirconium ⁇
  • a solution of lid in toluene (ZrO.0 ⁇ ⁇ ) was prepared in the same manner as in Example 15 except that 4.8 «> toluene was used in 10.5 ( ⁇ ).
  • Example 15 bis (cyclopentagenenyl) zirconium dichloride in a toluene solution (ZrO.04aio Z ⁇ was 12.0 l ⁇ £), and the aluminoxane synthesized in Example 1 in a toluene solution ( ⁇ 2.55 mo) was used. 6.3) and 1.7 »of toluene were added, and the mixture was stirred at 22 with 30 minutes to obtain a dark yellow transparent solution '.
  • Example 1 Toluene 50 OtD in 2 ⁇ stainless steel auto crepe sufficiently substituted with nitrogen The aluminum oxane synthesized in Example 1 was converted to aluminum atom by 1 miggram atom and triisobutylaluminum 2 mi. Remol was charged. Furthermore, was 51 S cm 2 ⁇ gauge pressure in at to HitoshiIri propylene 3 0.
  • Polymerization was performed in the same manner as in Example 18 except that triisobutylaluminum was not used in the polymerization in Example 18, and a 2.4 s polymer was obtained.
  • the temperature was raised to 40, and the reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed by distillation to obtain a white solid aluminoquin 13s.
  • the molecular weight determined by the freezing point depression in ⁇ - benzene of 33 s was 33. It was 0, and the m value shown in the sensitizer component [ ⁇ ] was 14.
  • Hexane 90 and 1-hexane 100 m were charged into a 2 stainless steel autolave sufficiently purged with nitrogen, and the temperature was raised to 45. Thereafter, 1-15 mol of tris-butylaluminum, and zirconium catalyst prepolymerized with ethylene, were charged at 0.015 mg atoms in terms of zirconium atoms. Furthermore, the temperature was raised to 60, and ethylene was introduced into the firing tank to initiate polymerization. Ethylene was continuously supplied so that the total pressure was kept at 7 ksZC Ci 2 -gauge, and polymerization was carried out at 70 at 2 hours.
  • the polymer slurry was added to a large excess of methanol, separated, and dried under reduced pressure at 80 ° C. for 12 hours.
  • a polymer having a ⁇ / ⁇ ⁇ ⁇ ⁇ ⁇ of 2.98, a bulk density of 0.33 g / coi 3 , and a room temperature n-decane soluble part of 0.31 u / t% was obtained at a yield of 0.11.2 s.
  • Table 5 shows the polymerization conditions and the like.
  • Example 13 was carried out in the same manner as in Example 13 except that the amount of prepolymerized ethylene was 0.66 g per 1 g of the catalyst.
  • Example 20 was carried out in the same manner as in Example 20, except that isobutyl aluminum was not used. Table 6 shows the results.
  • Sodium chloride (Wako Pure Chemical Industries, Ltd.) 250 s was charged into 2 stainless steel autoclaves sufficiently purged with nitrogen, and dried under reduced pressure at 3 CTC for 1 hour. Thereafter, the system was cooled to 65 and the system was replaced with ethylene. One millimol of triisobutylaluminum was read, and the zirconium solvent produced in Example 13 was converted to zirconium atoms by 1.5 milligram atoms and 1-hexene 1 were added. Polymerization was started with a total pressure of 8 kg / cm 2 ⁇ , taking into account ethylene.
  • Example 2 Triisobutyl aluminum and a zirconium catalyst were added at 75 without using 1-hexane in the polymerization of 1, and at 80 at 1 hour. Except having carried out polymerization, it carried out similarly to Example 21. Table 6 shows the results.
  • Example 23 to 26 Triisobutyl aluminum and a zirconium catalyst were added at 75 without using 1-hexane in the polymerization of 1, and at 80 at 1 hour. Except having carried out polymerization, it carried out similarly to Example 21. Table 6 shows the results.
  • Example 27 was performed in the same manner as in Example 27 except that isobutyl aluminum was not used. Table 6 shows the results.
  • Toluene 50 is added to a glass auto crepe of 1 volume with sufficient nitrogen replacement. Then, a mixed gas of ethylene and brovirene (120 £ / hr and 80 / hr, respectively) was passed, and the mixture was allowed to stand at 2 O'C for 10 minutes. After that, 0.5 mmol of tributylbutylaluminum was added, and after 5 minutes, 0.25 mmol atom of aluminoxane was converted to aluminum atom, and then bis (cyclopi-pentagenenyl) phen / xyzirconium monochloride was 2.5 ⁇ 1 0 3 was initiated Mi Rimoru added polymerization.
  • a mixed gas of ethylene and brovirene 120 £ / hr and 80 / hr, respectively
  • Example 28 was carried out in the same manner as in Example 28 except that triisobutylaluminum was not used in the polymerization in Example 28, but no polymer was obtained.
  • Example 28 was performed in the same manner as in Example 28 except that the catalyst component (A) prepared above was used instead of bis (cyclopentagenenyl) phenoxyzirconium monochloride.
  • Example 33 was carried out in the same manner as in Example 33 except that triisobutylaluminum was not used in the polymerization of Example 33, but almost no polymer was obtained.
  • Example 41 The procedure of Example 41 was repeated, except that 75 was replaced with 1-hexene instead of 4-methyl-1-pentene in the polymerization of 1. MFi l.01 g / OmiiK density 0.8 9 1 A polymer of 2.79 28.5 S was obtained.
  • Example 41 The polymerization was carried out in the same manner as in Example 41 except that isobutyl aluminum was not used in the polymerization of Example 1. MFR 1.94 g / l Otoin, density 0.908 g / ctfl 3 , ⁇ / ⁇ 2.95, a polymer with a soluble fraction at room temperature and a weight fraction of 1. l wt% —2.5 S was obtained.

Abstract

Procédé consistant à utiliser un catalyseur comprenant un catalyseur à base d'un métal de transition, un aluminoxane et un organo-aluminium. Dans ce procédé, un catalyseur contenant une faible quantité dudit aluminoxane est utilisé pour obtenir une excellente activité de polymérisation. Ce procédé permet de produire un polymère possédant une distribution étroite des poids moléculaires et un copolymère d'oléfine possédant une distribution étroite des poids moléculaires. On obtient également une distribution étroite de la composition dans la copolymérisation de deux ou plusieurs oléfines.
PCT/JP1987/000696 1986-09-24 1987-09-24 Procede de polymerisation d'olefines WO1988002378A1 (fr)

Priority Applications (3)

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AT87906209T ATE89836T1 (de) 1986-09-24 1987-09-24 Polymerisierungsverfahren fuer olefine.
KR1019880700560A KR920001352B1 (ko) 1986-09-24 1987-09-24 올레핀의 중합방법
DE8787906209T DE3786013T2 (de) 1986-09-24 1987-09-24 Polymerisierungsverfahren fuer olefine.

Applications Claiming Priority (8)

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JP61/223781 1986-09-24
JP22378186 1986-09-24
JP61/231242 1986-10-01
JP23124286A JPH0780931B2 (ja) 1986-10-01 1986-10-01 オレフインの重合方法
JP61231243A JPH0780937B2 (ja) 1986-10-01 1986-10-01 オレフインの重合方法
JP61/231243 1986-10-01
JP61293446A JP2502071B2 (ja) 1986-09-24 1986-12-11 オレフインの重合方法
JP61/293446 1986-12-11

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EP0406912B1 (fr) 1994-11-30
DE3752260D1 (de) 1999-04-22
EP0594218B1 (fr) 1999-03-17
ATE89836T1 (de) 1993-06-15
ATE114678T1 (de) 1994-12-15
DE3786013T2 (de) 1993-09-02
EP0812862B1 (fr) 2002-11-13
DE3750818T2 (de) 1995-04-20
ATE177759T1 (de) 1999-04-15
ATE227742T1 (de) 2002-11-15
EP0406912A3 (en) 1991-01-23
EP0812862A2 (fr) 1997-12-17
EP0406912A2 (fr) 1991-01-09
EP0594218A1 (fr) 1994-04-27
DE3752260T2 (de) 1999-09-02
DE3786013D1 (de) 1993-07-01
EP0287666A1 (fr) 1988-10-26
DE3750818D1 (de) 1995-01-12
EP0287666A4 (fr) 1988-11-07
EP0287666B1 (fr) 1993-05-26
DE3752359T2 (de) 2003-07-31
EP0812862A3 (fr) 1998-04-29
DE3752359D1 (de) 2002-12-19

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